Highly repellent carpet protectants

ABSTRACT

Carpet protectants comprising an aqueous dispersion comprising  
     A. a partially fluorinated urethane polymer having at least one urea linkage, which compound is the product of the reaction of: (1) at least one organic polyisocyanate containing at least three isocyanate groups; (2) at least one fluorochemical compound which contains per molecule (a) a single functional group having one or more Zerewitinoff hydrogen atoms and (b) at least two carbon atoms, each of which is attached to at least two fluorine atoms; and (3) water in an amount sufficient to react with from about 5% to about 60% of the isocyanate groups in said polyisocyanate;  
     B. a non-fluorinated cationic surfactant; and  
     C. a non-fluorinated nonionic surfactant are disclosed.

BACKGROUND OF THE INVENTION

[0001] Early fluorocarbon carpet protectant treatments were typicallyformulated within cationic surfactant systems. With the advent of theuse of anionic compositions to provide stain resistance in the cationictreatment, the problem of tip staining arose. When a carpet, pretreatedwith a stain resist, is treated with a cationic or cationicallydispersed fluorochemical repellant, sometimes localized staining canoccur on areas of the carpet fibers where the fluorochemical repellanthas been deposited. In the industry, this is termed tip-staining. Tipstaining is believed due to residues of cationic material on the carpet,the residues providing staining sites for acid dyes, such as caused byspills of soft drinks colored with the acid dye FD&C Red No. 40.

[0002] To address the tip staining problem anionic surfactant systemswere developed and employed for carpet soil resists, but such surfactantsystems compromised repellency. Kirchner in U.S. Pat. Nos. 5,414,111 and5,565,564 has described certain polyfluorourethane compounds forproviding oil and water repellent properties to a carpet substrate. Whenthese polyfluorourethane compounds were applied to carpet substrates asaqueous dispersions using anionic surfactants, tip staining was not aproblem. However, an ideal carpet protectant would exhibit higher levelsof repellency, towards both oily and aqueous soils, than is provided bythe existing art. With such higher levels of repellency, the soils failto wet the fibers, and are thus readily removed.

[0003] Thus there is a need for carpet protectant formulations thatimprove repellency without either causing tip-staining or gellingproblems, or detracting from the compatibility of anionic formulations.The present invention provides such formulations.

SUMMARY OF THE INVENTION

[0004] The present invention comprises an aqueous dispersion comprising

[0005] A. a partially fluorinated urethane polymer having at least oneurea linkage, which compound is the product of the reaction of: (1) atleast one organic polyisocyanate containing at least three isocyanategroups; (2) at least one fluorochemical compound which contains permolecule (a) a single functional group having one or more Zerewitinoffhydrogen atoms and (b) at least two carbon atoms, each of which isattached to at least two fluorine atoms; and (3) water in an amountsufficient to react with from about 5% to about 60% of the isocyanategroups in said polyisocyanate;

[0006] B. a non-fluorinated cationic surfactant; and

[0007] C. a non-fluorinated nonionic surfactant.

[0008] Such dispersions provide a high level of oil repellency, waterrepellency and soil resistance when applied to fibrous substrates suchas carpets.

[0009] The present invention further comprises a method for providingwater and oil repellency to a substrate comprising application to thesubstrate of a dispersion as described above.

[0010] The present invention further comprises a substrate treated witha dispersion as described above.

DETAILED DESCRIPTION

[0011] Hereinafter trademarks are shown in upper case.

[0012] The present invention comprises partially fluorinated urethanepolymers dispersed in water using mixtures of cationic and nonionicsurfactants. The dispersions of this invention, when applied to carpets,provide improved water repellency, oil repellency, and soil resistance,compared with carpets treated with the dispersions of partiallyfluorinated urethane polymers utilizing anionic surfactants. Carpetsubstrates to which the partially fluorinated urethane polymerdispersions of the present invention include carpets containing fibersof nylon, wool, polyester, poly(trimethylene terephthalate), polyolefin,cotton, jute, sisal, and the like, and mixtures thereof. Unexpectedly,some dispersions of the present invention are less prone to gelling inadmixture or contamination with some dispersions containing anionicsurfactants.

[0013] Additionally, the partially fluorinated urethane polymerdispersions of the present invention are substantially free of volatileorganic compounds (VOC), containing less than 1% VOC by weight, incontrast with the emulsions of partially fluorinated urethane polymersused in the prior art. VOCs in formulations that are subsequently driedare potential environmental air pollutants. They also contribute toworkplace hazards, such as potential flammability and worker exposureconcerns, and are thus undesirable.

[0014] The partially fluorinated urethane polymers used in the presentinvention comprise compounds having at least one urea linkage permolecule which compounds are derived from: (1) at least onepolyisocyanate or mixture of polyisocyanates which contains at leastthree isocyanate groups per molecule, (2) at least one fluorochemicalcompound which contains per molecule (a) a single functional grouphaving one or more Zerewitinoff hydrogen atoms and (b) at least twocarbon atoms, each of which is attached to at least two fluorine atoms,and (3) water in an amount sufficient to react with from about 5% toabout 60% of the —NCO groups in the polyisocyanate. In a preferredembodiment, the amount of water is sufficient to react with about 10% toabout 40% of the isocyanate groups in the polyisocyanate, and mostpreferably, between about 15% and about 30%.

[0015] A Zerewitinoff hydrogen atom is an active hydrogen in an organiccompound (in a group such as a —OH, —COOH, ═NH, etc. Paul Karrer, in theEnglish Translation of “Organic Chemistry”, published by Elsevier, 1938,page 135, provides further details. Such hydrogen atoms are measuredusing the Zerewitinoff method wherein the organic compound is reactedwith a CH₃Mg halide to liberate CH4 which, measured volumetrically,gives a quantitative estimate of the active hydrogen content of thecompound. Primary amines give 1 mole of CH₄ when reacted in the cold;usually 2 moles when heated. For purposes of this invention, it isassumed that a primary amine provides one active hydrogen as defined byZerewitinoff et al.

[0016] A wide variety of fluorochemical compounds that contain a singlefunctional group can be used so long as each fluorochemical compoundcontains at least two carbon atoms, and each carbon atom is attached toat least two fluorine atoms. For example, the fluorochemical compoundcan be represented by the formula:

R^(f)—R_(k)—X—H

[0017] wherein

[0018] R^(f) is a monovalent aliphatic group containing at least twocarbon atoms, each of which is attached to at least two fluorine atoms;

[0019] R is a divalent organic radical;

[0020] k is 0 or 1; and

[0021] X is —O—, —S—, or —N(R³) in which R³ is H, alkyl containing 1 to6 carbon atoms, or a R^(f)—R_(k)— group.

[0022] In a more specific embodiment, the fluorochemical compound whichcontains a single functional group can be represented by the formula:

R^(f)—R_(k)—R²—X′—H

[0023] wherein

[0024] R^(f) and k are as defined above;

[0025] R is the divalent radical: —C_(m)H_(2m)SO—, —C_(m)H_(2m)SO₂—,—SO₂N(R³)—, or —CON(R³)— in which m is 1 to 22 and R³ is H or alkyl of 1to 6 carbon atoms;

[0026] R² is the divalent linear hydrocarbon radical: —C_(n)H_(2n)—which can be optionally end-capped by

[0027]  in which n is 0 to 12, p is 1 to 50, and R⁴, R⁵ and R⁶ are thesame or different H or alkyl containing 1 to 6 carbon atoms; and

[0028] X′ is —O—, —S—, or —N(R⁷)— in which R⁷ is H, alkyl containing 1to 6 carbon atoms or a R^(f)—R_(k)—R²— group.

[0029] More particularly, R^(f) is a fully-fluorinated straight orbranched aliphatic radical of 3 to 20 carbon atoms.

[0030] In a preferred embodiment, the fluorochemical compound whichcontains a single functional group can be represented by the formula:

R^(f)—(CH₂)_(q)—X—H

[0031] wherein

[0032] X is —O—, —S—, or —N(R⁷)— in which R⁷ is H, alkyl containing 1 to6 carbon atoms or a R^(f)—R_(k)—R²— group.

[0033] R^(f) is a mixture of perfluoroalkyl groups, CF₃CF₂(CF₂)_(r) inwhich r is 2 to 18; and

[0034] q is 1, 2 or 3.

[0035] In a more particular embodiment, R^(f) is a mixture of saidperfluoroalkyl groups, CF₃CF₂(CF₂)_(r); and r is 2, 4, 6, 8, 10, 12, 14,16, and 18. In a preferred embodiment, r is predominantly 4, 6 and 8. Inanother preferred embodiment, r is predominantly 6 and 8. The formerpreferred embodiment is more readily available commercially and istherefore less expensive, while the latter may provide improvedproperties. In a typical mixture of such perfluoroalkyl groups, thecompounds will have the following approximate composition in relation totheir CF₃CF₂(CF₂)_(r) groups:

[0036] 0% to 3% wherein r=2,

[0037] 27% to 37% wherein r=4,

[0038] 28% to 32% wherein r=6,

[0039] 24% to 20% wherein r=8,

[0040] 8% to 13% wherein r=10,

[0041] 3% to 6% wherein r=12,

[0042] 0% to 2% wherein r=14,

[0043] 0% to 1% wherein r=16, and

[0044] 0% to 1% wherein r=18.

[0045] Representative fluoroaliphatic alcohols that can be used for thepurposes of this invention are:

C_(s)F_((2s+1))(CH₂)_(t)OH,

C_(s)F_((2s+1))CON(R⁸)(CH₂)_(t)OH,

C_(s)F_((2s+1))SO₂N(R⁸)(CH₂)_(t)OH, and

[0046] wherein

[0047] s is 3 to 20;

[0048] t is 1 to 12;

[0049] each of R⁸ and R⁹ is independently H or alkyl containing 1 to 6carbon atoms.

[0050] In another embodiment of the invention, a nonfluorinated organiccompound which contains a single functional group can be used inconjunction with one or more of said fluorochemical compounds. Usuallyin this embodiment, between about 1% and about 60% of the isocyanategroups of the polyisocyanate are reacted with at least one suchnonfluorinated compound. For example, said nonfluorinated compound canbe represented by the formula:

R¹⁰—(R¹¹)_(k)—YH

[0051] wherein

[0052] R¹⁰ is a C₁-C₁₈ alkyl, a C₁-C₁₈ omega-alkenyl radical or a C₁-C₁₈omega-alkenoyl;

[0053] R¹¹ is

[0054]  in which R⁴, R⁵ and R⁶ are the same or different H or alkylradical containing 1 to 6 carbon atoms and p is 1 to 50;

[0055] Y is —O—, —S—, or —N(R³)— in which R³ is H or alkyl containing 1to 6 carbon atoms; and

[0056] k and p are as defined above.

[0057] For example, the nonfluorinated compound can be an alkanol or amonoalkyl or monoalkenyl ether of a polyoxyalkylene glycol. Particularexamples of such compounds include stearyl alcohol, the monoalkyl etherof polyoxyethylene glycol, the mono-allyl or -methallyl ether ofpolyoxyethylene glycol, and the like.

[0058] Any polyisocyanate having three or more isocyanate groups can beused for the purposes of this invention. For example, one can usehexamethylene diisocyanate homopolymers having the formula:

[0059] wherein x is an integer equal to or greater than 1, preferablybetween 1 and 8. Because of their commercial availability, mixtures ofsuch hexamethylene diisocyanate homopolymers are preferred for purposesof this invention. Also of interest are hydrocarbon diisocyanate-derivedisocyanurate trimers that can be represented by the formula:

[0060] wherein R¹² is a divalent hydrocarbon group, preferablyaliphatic, alicyclic, aromatic or arylaliphatic. For example, R¹² can behexamethylene, toluene or cyclohexylene, preferably the first. Otherpolyisocyanates useful for the purposes of this invention are thoseobtained by reacting three moles of toluene diisocyanate with1,1,1-tris-(hydroxymethyl)-ethane or 1,1,1-tris(hydroxymethyl)-propane.The isocyanurate trimer of toluene diisocyanate and that of3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate are otherexamples of polyisocyanates useful for the purposes of this invention,as is methine-tris-(phenylisocyanate). Also useful for the purposes ofthis invention is the polyisocyanate having the formula:

[0061] The partially fluorinated urethane polymers of the invention areprepared by reacting: (1) at least one polyisocyanate or mixture ofpolyisocyanates which contains at least three isocyanate groups permolecule with (2) at least one fluorochemical compound which containsper molecule (a) a single functional group having one or moreZerewitinoff hydrogen atoms and (b) at least two carbon atoms, each ofwhich is attached to at least two fluorine atoms. Thereafter theremaining isocyanate groups are reacted with water to form one or moreurea linkages. Usually between about 40% and about 95% of the isocyanategroups will have been reacted before water is reacted with thepolyisocyanate. In other words, the amount of water generally issufficient to react with from about 5% to about 60% of the isocyanategroups in the polyisocyanate. Preferably, between about 60% and about90% of the isocyanate groups have been reacted before water is reactedwith the polyisocyanate, and most preferably between about 70% and about85% of the isocyanate groups have been reacted prior to reaction ofwater with the polyisocyanate. Thus, in a preferred embodiment theamount of water is sufficient to react with about 10% to about 40% ofthe isocyanate groups, most preferably between about 15% and about 30%.

[0062] In one embodiment, water-modified fluorochemical carbamates havebeen prepared by the sequential catalyzed reaction of DESMODUR N-100,DESMODUR N-3200 or DESMODUR N-3300, or mixtures thereof, with astoichiometric deficiency of a fluoroalkyl compound containing onefunctional group, and then with water. DESMODUR N-100 and DESMODURN-3200 are hexamethylene diisocyanate homopolymers commerciallyavailable from Bayer Corporation (Pittsburgh, Pa.). Both presumably areprepared by the process described in U.S. Pat. No. 3,124,605 andpresumably to give mixtures of the mono-, bis-, tris-, tetra- and higherorder derivatives which can be represented by the general formula:

[0063] wherein x is an integer equal to or greater than I, preferablybetween 1 and 8. Average Equivalent Typical Properties Weight NCOContent. % DESMODUR N-100 191 22.0 DESMODUR N-3200 181 23.2

[0064] The typical —NCO content of DESMODUR N-100 approximates thatlisted for a SR1 International Report (Isocyanates No. ID, July, 1983,Page 279) hexamethylene diisocyanate homopolymer with the followingcomposition: Product Composition Weight % Hexamethylene diisocyanate 0.1Monobiuret 44.5 Bisbiuret 17.4 Trisbiuret 9.5 Tetrabiuret 5.4 HigherMol. Wt. Derivatives 23.1 NCO Content 21.8

[0065] Based on its average equivalent weight and NCO content, thecomparative bis-, tris-, tetra-, etc., content of DESMODUR N-3200 shouldbe less than that of the N-100 product. DESMODUR N-3300 is ahexamethylene diisocyanate-derived isocyanurate trimer, which can berepresented by the formula:

[0066] The water-modified partially fluorinated urethane polymers aretypically prepared by first charging the polyisocyanate, the fluoroalkylcompound and a dry organic solvent such as methylisobutylketone (MIBK)to a reaction vessel. The order of reagent addition is not critical. Thespecific weight of aliphatic polyisocyanate and fluoroalkyl compoundscharged is based on their equivalent weights and on the working capacityof the reaction vessel and is adjusted so that all Zerewitinoff activehydrogens charged will react with some desired value between about 40%and about 95% of the total NCO groups charged. The weight of dry solventis typically between about 15% and about 30% of the total charge weight.The charge is agitated under nitrogen and heated to 40°-70° C. Acatalyst, typically dibutyltindilaurate per se, or as a solution inmethylisobutylketone (MIBK), is added in an amount which depends on thecharge, but is usually small, e.g. 1 part per 2000 to 3000 parts of thepolyisocyanate. After the resultant exotherm, the mixture is agitated ata temperature between about 65° and about 105° C. for 2-20 hours fromthe time of the catalyst addition. Then, after its temperature isadjusted to between about 550 and about 90° C., the mixture is treatedwith water per se or with wet MIBK for an additional 1 to 20 hours. Theresultant product is converted to a surfactant-stabilized dispersion.

[0067] The partially fluorinated urethane polymers, dissolved ordispersed in hot solvent are emulsified in water using surfactants,using equipment such as a sonnicator, homogenizer, microfluidizer, highshear blending equipment and the like. The emulsion is cooled and thesolvent stripped off by distillation to form the aqueous dispersion. Thedispersion is prepared using mixtures of cationic and nonionicsurfactants.

[0068] Suitable cationic surfactants for the practice of the presentinvention are listed below, under three categories. Specific examplesand preferred examples of cationic surfactants are listed, but thepractice of this invention is not limited to the specific citedsurfactants, which are provided only as examples.

[0069] Category 1 comprises salts of protonated amines. The acids withwhich these amines can be protonated to form ammonium salts include, butare not limited to, hydrochloric and acetic (hereinafter abbreviated asHOAc) acids. Preferred cationic surfactants are alkyl dimethyl amines(e.g., ARMEEN DM12D/HOAc and preferably ARMEEN DM18D/HOAc), dialkylmethyl amines, alkyl ethoxylated amines, alkyl diamines and theirethoxylates.

[0070] Category 2 comprises quaternary ammonium salts. Such quaternaryammonium salts are typically produced by alkylation of amines, includingthose listed above. Alkylating agents frequently include, but are notlimited to, methyl chloride, dimethyl sulfate, diethyl sulfate, andbenzyl chloride. Additional useful cationic surfactants are alkyltrimethyl ammonium salts (such as ARQUAD 12-50, ARQUAD 16-50, ARQUAD18-50, and ARQUAD C-50); dialkyl dimethyl ammonium salts (such as ARQUADHTL8 (W) MS-85 and the preferred ARQUAD 2C-75 and ARQUAD 2HT-75),specifically dialkyl dimethyl ammonium chloride; alkyl methylethoxylated ammonium (such as ETHOQUAD C/25 and ETHOQUAD 18/25); alkyldimethyl benzyl ammonium; dialkyl methyl benzyl ammonium; alkyl,alkylamidomethyl, and carboalkoxy pyridinium (with and without ringsubstitution); alkyl quinolinium; alkyl isoquinolinium; N,N-alkylmethylpyrollidinium; amidoimidazolinium; amido ammonium; and quaternaryammonium salts of alkyl diamines and their ethoxylates.

[0071] Category 3 comprises alkyl dimethyl amine oxide, dialkyl methylamine oxide, and alkyl diamine oxide.

[0072] Thus the cationic surfactant of any category is typicallyselected from the group consisting of at least one of a protonated alkyldimethyl amine salt, protonated dialkyl methyl amine salt, protonatedalkyl ethoxylated amine salt, protonated alkyl diamine salt, protonatedalkyl ethoxylated diamine salt, alkyl trimethyl ammonium salt, dialkyldimethyl ammonium salt, alkyl methyl ethoxylated ammonium salt, alkyldimethyl benzyl ammonium salt, dialkyl methyl benzyl ammonium salt,alkyl pyridinium salt, alkylamidomethylpyridinium salt, carboalkoxypyridinium salt, alkyl quinolinium salt, alkyl isoquinolinium salt,N,N-alkyl methyl pyrollidinium salt, amidoimidazolium salt, and amidoammonium salt. Alternatively the cationic surfactant is selected from aquaternary ammonium salt of alkyl diamine, ethoxylate of quaternaryammonium salt of alkyl diamine, alkyl dimethyl amine oxide, dialkylmethylamine oxide, and alkyl diamine oxide.

[0073] Suitable nonionic surfactants for the practice of the presentinvention are ethylene oxide condensates. Examples of types of suchethylene oxide condensates include condensates with esters of fattyacids and polyhydric alcohols (such as sorbitan esters, e.g., TWEEN 80);with fatty acid alkanol amides (such as amides of fatty acids anddiethanol amine, e.g., AMIDOX C-5); with alkyl phenols (such asisooctylphenol, e.g., IGEPAL CA-720); with a fatty acid (such as astearate, e.g., MAPEG 600MS); with a linear fatty alcohol (such asMERPOL HCS, BRIJ 35, BRIJ 56, BRIJ 58, BRIJ 76, or BRIJ 700); with abranched fatty alcohol (such as MERPOL SE or TERGITOL 15-S-1 5); andwith poly(oxypropylene) block-copolymers (such as PLURONIC L81). Morepreferred are nonionic surfactants having the structure of Formula A

C_(x)H_((2x+1))O—(CH₂CH₂O)_(n)—H  Formula A

[0074] wherein x is 12 to 18 and n is 5 to 100. Most preferred arepolyethoxylated linear alcohols.

[0075] The above listed surfactants are commercially available from thefollowing sources. AMIDOX C-5 and WAQE are products of the StepanCompany (Northfield, Ill.). ARMEEN, ETHOQUAD, and ARQUAD products wereobtained from Akzo Nobel (Chicago, Ill.). DESMODUR N-100, N-3200, andN-3300 are described above and are available from Bayer Corporation(Pittsburgh, Pa.). IGEPAL CA-720 may be obtained form the AldrichChemical Company (Milwaukee, Wis.). MAPEG 600MS is a product of MazerChemicals, Inc. (Gurnee, Ill.). MERPOL HCS and MERPOL SE are products ofE. I. du Pont de Nemours and Co. (Wilmington, Del.). PLURONIC L81 is aproduct of BASF Corporation (Mt. Olive, N.J.). TERGITOL 15-S-15 is aproduct of Dow Chemical Company (Midland, Mich.). BRIJ and TWEENproducts are from ICI Americas Inc. (Bridgewater, N.J.).

[0076] Most quaternary ammonium salts exhibit antimicrobial properties.They are effective agents against a variety of bacteria, fungi, andviruses, while presenting a low order of human toxicity. Thus the use ofquaternary ammonium salts in the practice of this invention caneliminate the need for added antimicrobials for dispersion stability andstorage.

[0077] The amount of surfactant or surfactants, by weight and based onthe amount of the partially fluorinated urethane polymer, is from about1% to about 12% and preferably from about 1% to about 5% of the cationicsurfactant, and from about 0.5% to about 12%, and preferably from about0.5% to about 3% of the nonionic surfactant. Thus the preferred totalsurfactant is from about 1.5% to about 8%, based on the weight ofpartially fluorinated urethane polymer.

[0078] The concentration of the partially fluorinated urethane polymerdispersion is adjusted and applied at a wet pick up rate sufficient toprovide from about 100 to about 2000 micrograms, and preferably fromabout 200 to about 800 micrograms fluorine per gram of dry fibersubstrate to which it is applied. The goal fluorine level (micrograms offluorine per gram of carpet fiber pile) is the product of (1) theapplication rate of the partially fluorinated polyurethane emulsion ontothe carpet pile and (2) the fluorine weight concentration of thepartially fluorinated polyurethane emulsion. The application rate (1) ofthe partially fluorinated polyurethane emulsion onto the carpet pile isthe product of (a) wet pick up of the application bath of the partiallyfluorinated polyurethane emulsion in water based on the face weight ofthe carpet, and (b) the concentration by weight of the partiallyfluorinated polyurethane emulsion in water.

[0079] The present invention further comprises a method for providingwater repellency and oil repellency to a substrate comprisingapplication to the substrate of a dispersion as described above. Theaqueous dispersion formulations of the present invention can be appliedto suitable substrates by a variety of methods. Examples of such methodsinclude, but are not limited to, beck dying procedures, continuousdyeing procedures, thread-line applications, brushing, dipping,spraying, padding, roll-coating, foaming or the like. The aqueousdispersion formulations of this invention can be applied to thesubstrate as such or in combination with other textile orfluorofinishes, stainblockers, processing aids, lubricants, anti-stains,etc. The formulations can also be blended with other agents that haveoil/water repellency and soil release properties and applied to fibersor fabrics. They can be applied to dyed and undyed carpeting and othertextile substrates.

[0080] In carpet mills, different chemicals often share common supplylines and mixing equipment, if only briefly. Compatibility between thevarious antistatic agents, antimicrobial agents, stainblockers,fluorochemicals, and other chemical treatments for carpet protectionsimplifies the carpet manufacturing process and chemical applicationequipment. The overall compatibility of fluorochemical protectants is ameasure of how many different antistatic agents, antimicrobial agents,stainblockers, fluorochemicals, and other chemical treatments for carpetprotection are compatible with the fluorochemical protectant. Mostanionic emulsions and dispersions are incompatible with most cationicemulsions and dispersions. An incompatibility between two emulsions ordispersions can be observed as separation or coagulation of the mixtureof chemical treatments. One of the advantages of the compositions of thepresent invention is the compatibility with a wide variety of carpettreatment chemicals.

[0081] A wide range of stain resists and soil resists are suitable foruse in the practice of the present invention. Suitable stain resists arepolymers containing phenol-formaldehyde, methacrylic acid, maleic acid,sulfonated fatty acids, and blends of the above. Suitable soil resistsare polymers containing fluorochemical residues with the most preferredbeing cationically dispersed. The use of cationic fluorochemicals incombination with anionic stain resists typically gives better fluorineretention. Suitable stain resists for the practice of this inventioninclude, but are not limited to, phenol formaldehyde polymers orcopolymers such as CEASESTAIN and STAINAWAY (from American EmulsionsCompany, Inc., Dalton, GA), MESITOL (from Bayer Corporation, Pittsburgh,Pa.), ERIONAL (from Ciba Corporation, Greensboro, NC), INTRATEX (fromCrompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (fromDyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar ChemicalCorporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I. duPont de Nemours and Company, Wilmington, Del.); polymers of methacrylicacid such as the SCOTCHGARD FX series carpet protectors (from 3MCompany, St. Paul, Minn.); and sulfonated fatty acids from RocklandReact-Rite, Inc., Rockmart, Ga.). Suitable soil resists for the practiceof the present invention include, but are not limited to, fluorochemicalemulsions such as AMGUARD (from American Emulsions Company, Inc.,Dalton, Ga.), SOFTECH (from Dyetech, Inc., Dalton, Ga.), LANAPOL (fromLenmar Chemical Corporation, Dalton, Ga.), SCOTCHGARD FC series carpetprotectors (from 3M Company, St. Paul, Minn.), NK GUARD (from Nicca USA,Inc., Fountain Head, NC), UNIDYNE (from Diakin America, Inc., Decatur,Ala.), and ZONYL 555, N-130 and N-119 (from E. I. du Pont de Nemours andCompany, Wilmington, Del.).

[0082] The present invention further comprises a substrate having acoating on its surface of a dispersion as described above. Suitablesubstrates for the application of the products of this invention arefibrous substrates such as carpets, rugs, and the yarns and fibers usedto make such carpets and rugs. Specific representative examples includedyed and undyed yarns and fibers containing fibers of nylon, wool,polyester, poly(trimethylene terephthalate), polyolefin, cotton, jute,sisal, and the like, and mixtures thereof. Such substrates areespecially suitable for treatment with the compositions of thisinvention to provide products having a high repellency to oil and water.The treated substrates are also relatively unaffected by the action ofheat, air and light. Materials rendered oil and water-repellent by theproducts of this invention retain a high portion of the originalrepellency after cleaning. The partially fluorinated urethane polymersof this invention impart oil-, water-, and soil-repellency properties tofibrous substrates.

[0083] Two types of substrates are of particular interest in accordancewith the present invention. One of those is carpeting, particularlynylon carpeting, to which compounds of the present invention are appliedso as to impart oil-, water- and soil-repellency. The other class ofsubstrates to which it is particularly advantageous to apply thecompounds of the present invention so as to impart soil-releaseproperties includes those prepared from polyamide fibers (such asnylon), cotton and blends of polyester and cotton. Of particularinterest is polyamide carpeting, e.g. nylon carpeting.

Test Methods

[0084] The following Test methods were employed in the Examples.

[0085] Test Method 1: Soiling Evaluation

[0086] Materials:

[0087] The following materials are used. U.S. Stoneware BURUNDUMcylinders was from VWR Scientific Products, South Plainfield N.J. (smallcylinders 1.2 cm diameter, 1.2 cm height and medium cylinders 2 cmdiameter, 2 cm height). Cylindrical extruded ZYTEL nylon-6,6 pellets 0.2cm diameter, 0.3 cm height was from E. I. du Pont de Nemours and Co.,Wilmington, Del. AATCC standard soil is available from AmericanAssociation of Textile Chemists and Colorists, Research Triangle Park,NC. Soiled nylon pellets were prepared by combining 3 g of AATCCstandard soil and 1000 g of ZYTEL nylon-6,6 pellets in a container andtumble mixing for 20 minutes to insure a homogeneous coating of soil onthe pellets.

[0088] Equipment:

[0089] The following equipment is used. Vetterman drums are availablefrom A. Schonberg Gmbh & Co., Am Sportplatz, Germany, and the Vettermandrum operation is described in ISO test method TR-10361. The calorimeterfor measuring the visual change in soiling is manufactured by MinoltaCorp., Ramsey, N.J. The vacuum cleaner is a Hoover “Preferred” uprightmodel type “A”, 110 Volt, 7.2 amp from Maytag Corporation, Newton, Iowa.

[0090] Procedure:

[0091] To perform the soiling test, the carpet samples were placed inthe Vefterman drum. 1200 g of small, and 600 g of medium, BURUNDUMcylinders were added to the drum, together with 200 g of fresh nylonpellets and 100 g of soiled nylon pellets, and the opening in the faceof the Vetterman drum was closed with a PLEXIGLASS cover. The Vettermandrum was operated for 500 revolutions, after which the BURUNDUMcylinders and the dirty nylon pellets were removed. The carpet sampleswere removed and cleaned with the vacuum cleaner until no further soilwas removed. Typically 5 to 8 passes of the vacuum in two perpendiculardirections over the pile were necessary. This completed the firstVetterman drum cycle.

[0092] For the second cycle, the carpet samples were returned to theVetterman drum, together with the BURUNDUM cylinders and 200 g of thedirty nylon pellets from the previous soiling. An additional 100 g ofsoiled nylon pellets were added to the drum before covering the openingin the face of the Vetterman drum with the PLEXIGLASS cover. TheVetterman drum was then run for an additional 500 revolutions. TheBURUNDUM cylinders and the dirty nylon pellets were removed from thedrum. The carpet samples were removed and cleaned with the vacuumcleaner as before until no further soil was removed, completing thesecond cycle.

[0093] The above “second” cycle procedure was repeated until a total of10 soiling cycles, each with 500 Vetterman drum revolutions, werecompleted. Finally, color differences are evaluated using a Minoltacalorimeter and reported as Delta E. Delta E is a measure of soilretention based on the difference in reflectance between soiled andunsoiled carpet. Lower delta E values indicate superior soil resistanceand repellency.

[0094] Test Method 2: Oil and Water Repellency Tests

[0095] The oil repellency test is adapted from AATCC Test Method 118. Apiece of carpet is conditioned for a minimum of 2 hours at 23+/−2° C.and 65+/−10% relative humidity. Beginning with the lowest numbered testliquid (Repellency Rating No. 1), one drop (approximately 5 mm diameteror 0.05 mL volume) is placed on each of three locations at least 5 mmapart. The drops are observed for 10 seconds for the water-repellencytest, 30 seconds for the oil-repellency test. If, at the end of thoseperiods of time, two of the three drops are still spherical tohemispherical in shape with no wicking around the drops, three drops ofthe next higher numbered test liquid are placed on adjacent sites andobserved again for the specified periods of time. The procedure iscontinued until one of the test liquids results in two of the threedrops failing to remain spherical or hemispherical, or wetting orwicking occurs. The oil-repellency rating (OR) and the water-repellency(WR) rating of the carpet is the highest numbered test liquid for whichtwo of three drops remain spherical or hemispherical with no wicking forthe specified time. STANDARD WATER REPELLENCY TEST LIQUIDS Water-Repellency Composition (Volume %) Rating # (WR) Isopropanol Water 1 2 982 5 95 3 10 90 4 20 80 5 30 70 6 40 60 STANDARD OIL REPELLENCY TESTLIQUIDS Oil-Repellency Rating # (OR) Composition 1 NUJOL* 2 65/35NUJOL/n- hexadecane by volume at 21° C. 3 n-hexadecane 4 n-tetradecane 5n-dodecane 6 n-decane

[0096] Cherry KOOL-AID stain and repellency testing is conducted oncarpet samples 15 cm by 15 cm. Acid dye stain resistance was evaluatedusing a procedure based on the American Association of Textile Chemistsand Colorists (AATCC) Method 175-1991, “Stain Resistance: Pile FloorCoverings.” A staining solution was prepared by mixing water and sugarsweetened cherry KOOL-AID, according to package directions. KOOL-AID isa trademark of Kraft General Foods, Inc. The carpet sample to be testedwas placed on a flat non-absorbent surface and a hollow plastic cylinderhaving a 2-inch (5-cm) diameter was placed tightly over the carpetsample. Twenty ml of staining solution was poured into the cylinder andthe solution was allowed to absorb completely into the carpet sample.The cylinder was then removed and the stained carpet sample was allowedto sit undisturbed for 24 hours, after which it was rinsed thoroughlyunder cold tap water and squeezed dry. The carpet sample was thenvisually inspected and rated for staining according to AATCC Red 40Stain Scale. A KOOL-AID stain rating (KA) of 10 is excellent, showing novisible stain, whereas 1 is the poorest rating, comparable to anuntreated control sample.

[0097] Test Method 4: Mixing Compatibility

[0098] The compatibility of the partially fluorinated urethane polymerdispersions of the present invention was tested by mixing them withcommon carpet chemical treatments (stainblockers or fluorochemical soilresists) in a 1:1 volume ratio and observing any separation orcoagulation of the mixture. For each compatibility test, 5 mL of afluorochemical protectant of the present invention were combined with 5mL of an anionic stainblocker or fluorochemical soil resist. Thecombination of chemicals was shaken for 1 minute. Any separation orgelling after 1 hour was recorded. If no visible change in viscosity(gelling) or separation of the mixture was observed after 1 hour, thenthe compatibility of those two chemicals was judged “OK”. Otherwise, theincompatibility was described as “gelled” or “separated”. The partiallyfluorinated urethane polymer dispersions of the present invention aresubstantially more compatible with such anionic chemicals as is shown inTable 12.

EXAMPLES

[0099] In the Examples and Comparative Examples below, the carpettreatment variables for the application of the partially fluorinatedurethanes were designed to achieve about 500 to about 700 micrograms offluorine per gram of carpet fiber pile. Sources of chemicals are aspreviously listed above.

Example 1

[0100] The perfluoroalkylethyl alcohol (FA) used in this example had theformula F(CF₂)_(y)CH₂CH₂OH wherein y is predominately 6, 8, and 10. Ahexamethylene diisocyanate homopolymer (DESMODUR N-100), aperfluoroalkylethyl alcohol mixture (FA) in an amount sufficient toreact with 80% of the NCO group charge, and dry MIBK in an amount equalto 22% of the total charge weight were added to a reaction vessel,agitated under nitrogen and heated to 60°-65° C., whereupon a catalyticamount of dibutyltindilaurate was added. After the resultant exotherm,the reaction mixture was agitated at about 80°-85° C. for 2 hours fromthe time of the catalyst addition, and then treated with wet MIBK in anamount equal to a water ratio of 1.03. The diluted mixture was agitatedat about 65° C. for an additional 2 hours.

[0101] A solution/mixture of 48 g of MIBK and 52 g of partiallyfluorinated urethane polymer, prepared as described above, was melted atabout 60° C. A warm surfactant solution was prepared by mixing 2.08 g ofARQUAD 2HT-75 and 0.55 g of MERPOL SE with 87.85 g of deionized water.This aqueous surfactant solution was combined with the moltenMIBK/partially fluorinated urethane polymer mixture, and the compositionemulsified by sonnication. MIBK was removed by vacuum distillation toproduce a milky dispersion that was diluted to about 24% solids.

Examples 2-24

[0102] The procedure described above for Example 1 was followed toproduce Examples 2-24 using the partially fluorinated urethane polymerof Example 1 with different combinations of surfactants. The surfactantsused are listed in Table 1.

Comparative Examples C-G

[0103] Comparative examples C-G were prepared according to the procedurefor Example 1 using the partially fluorinated urethane polymer ofExample 1, except that no nonionic surfactant was used. TABLE 1Surfactants used in the preparation of Examples 2-23. Amount Non-ionicAmount Cationic Surfactant (g) Surfactant (g) Ex. #  2 ARQUAD 2HT-752.08 BRIJ 58 0.52  3 ARQUAD 2HT-75 2.08 BRIJ 76 0.52  4 ARQUAD 2C-752.08 BRIJ 35 0.52  5 ARQUAD 2C-75 2.08 MAPEG 0.52  6 ARMEEN DM18D1.56/0.3 MERPOL HCS 0.87  7 ARMEEN DM18D 1.56/0.3 BRIJ 35 0.52  8 ARMEENDM18D 1.56/0.3 BRIJ 58 0.52  9 ARMEEN DM18D 1.56/0.3 BRIJ 76 0.52 10ARQUAD 2C-75 2.08 MAPEG 0.52 11 ARQUAD 2C-75 2.08 BRIJ 58 0.52 12 ARQUAD2C-75 2.08 BRIJ 35 0.52 13 ARQUAD 2HT-75 2.08 BRIJ 58 0.52 14 ARMEENDM18D 1.56/0.3 BRIJ 58 0.52 15 ARQUAD 2HT-75 2.08 MERPOL SE 0.55 16ARMEEN DM12D 1.56/0.4 BRIJ 58 0.52 17 ARQUAD 18-50 3.12 BRIJ 58 0.52 18ETHOQUAD C/25 1.64 BRIJ 58 0.52 19 ARQUAD 2C-75 0.69 MAPEG 1.56 20ARQUAD 2C-75 1.39 MAPEG 1.04 21 ARQUAD 2C-75 2.08 MAPEG 0.52 22 ARQUAD2C-75 0.69 MAPEG 0.52 23 ARQUAD 2C-75 2.08 MAPEG 1.56 24 ARQUAD 2C-755.55 MAPEG 4.16 Comparative Examples C ARQUAD 18-50 5.20 NONE D ARQUAD2C-75 3.47 NONE E ARQUAD 2HT-75 3.47 NONE F ETHOQUAD 18/25 2.74 NONE GARMEEN DM18D/ 2.60/0.50 NONE HOAc

Comparative Example A

[0104] This example demonstrates a composition containing an anionicsurfactant. A solution of partially fluorinated urethane polymer wasproduced as described in Example 1. This solution was mixed with anaqueous solution of Witco 6094 (available from Witco Chemical Corp.,Houston Tex.) with the weight content of the surfactant equaling 6% ofthe weight of partially fluorinated urethane polymer. An emulsion ofthis mixture was generated via a homogenizer, and the organic solventwas removed by vacuum distillation to produce a milky dispersion ofpartially fluorinated urethane polymer in water. This dispersion wasdiluted to about 24% solids.

Comparative Example B

[0105] This example demonstrates a different partially fluorinatedurethane polymer composition combined with a cationic and a nonionicsurfactant.

[0106] Two and one half moles of a mixture of fluoroalcohols of theformula F(CF₂)_(y)CH₂CH₂OH, wherein y is predominantly 6, 8, and 10,were charged to a reaction vessel and under a nitrogen atmosphere heatedto 60-70° C. A 60 wt. % solution of one mole of DESMODUR N-3200 in MIBKwas added to the fluoroalcohol and the resulting reaction mixture wasagitated and allowed to cool to about 60-65° C., at which point acatalytic amount of dibutyltin dilaurate was added. After the resultingexotherm subsided, the reaction mixture was agitated an additional 2hours at 80-85° C. and one half mole of 3-chloro-1,2-propanediol (as a47.4% solution in MIBK) was added. The reaction mixture was heated at65° C. and agitated an additional 12 hours at which time it was dilutedto 54 wt. % solids with MIBK. The product was a mixture.

[0107] A molten solution/mixture of partially fluorinated urethanepolymer, prepared as described above, was washed with a 1.92% aqueoussolution of sodium chloride, after which, it was mixed with an aqueoussolution of ARQUAD 12-50 and MERPOL HCS (with the weight content of thesurfactants equaling 3% and 1%, respectively, of the weight of partiallyfluorinated urethane polymer). An emulsion of this mixture was generatedvia a homogenizer, and the organic solvent was removed by vacuumdistillation to produce a milky dispersion of partially fluorinatedurethane polymer in water. This dispersion was diluted to about 20%solids.

Examples 25-33

[0108] A dyed light blue 30 oz./yd² (1 kg/m²) tufted, cut pile carpet(made from twisted, SUPERBA heatset, 1150 DuPont fiber, from E. I. duPont de Nemours and Company, Wilmington, Del.) was passed through aflex-nip application of 250% by weight of a bath containing 16 g/L ofSR-500 Stain Resist (available from E. I. Du Pont de Nemours and Co.Inc, Wilmington, Del.). The carpet was steamed at 210-212° F. (99-100°C.) for 2.5 min. and washed with water. It was then vacuum extracted to50% wet pickup, and dried to a carpet face temperature of 300° F. (149°C.).

[0109] A 762 cm² carpet sample was moistened with 10 g of water using atrigger sprayer from WB Bottle Supply Co., Inc., Milwaukee, Wis. Thecarpet sample was then sprayed using a trigger sprayer with 22 g of amixture of 2.0 g of the partially fluorinated urethane polymerdispersion (as shown in Tables 2 and 3) and 100 g of water orapproximately 25% wet pick up based on the face weight of the carpet.The surface pile of the carpet was rolled with a small roller (7 cmwide) to mechanically spread the partially fluorinated urethane polymerdispersion coating across the entire carpet pile. The carpet sample wasdried an oven at 65° C. for 20 minutes then immediately placed in asecond oven at 150° C. and cured for 3 minutes. The carpet was cooledand conditioned for at least 4 hours at approximately 22° C. and 75%relative humidity prior to any evaluations. The goal fluorine level was550 micrograms of fluorine per gram of carpet fiber pile based on the0.5% application rate of the partially fluorinated urethane polymerdispersion onto the carpet pile, of an emulsion with a fluorine level of11% by weight. The 0.5% application rate onto the carpet pile is theproduct of 25% wet pick up of the 2% bath of the partially fluorinatedurethane polymer dispersion in water.

[0110] Aqueous dispersions of Examples 1-9 were applied to the carpetsamples prepared as described above. These samples were tested forrepellency, using Test Method 2, versus untreated control carpet samplesand carpet samples treated with Comparative Examples A and B. Theresults of these tests are presented in Tables 2 and 3. TABLE 2Comparison of repellency Dispersion Example used Surfactants OR WR 25Ex. 1 ARQUAD 2HT-75/MERPOL 3 5 SE 26 Ex. 2 ARQUAD 2HT-75/BRIJ 58 3 4 27Ex. 3 ARQUAD 2HT-75/BRIJ 76 3 4 Comparative Example A 0 4 ComparativeExample B 1 4 Untreated Control 0 0

[0111] TABLE 3 Comparison of repellency Dispersion Example usedSurfactants OR WR 28 Ex. 4 ARQUAD 2C-75/BRIJ 35 3 4 29 Ex. 5 ARQUAD2C-75/MAPEG 600MS 3 5 30 Ex. 6 ARMEEN DM18D-HOAc/MERPOL 4 5 HCS 31 Ex. 7ARMEEN DM18D-HOAc/BRIJ 35 5 5 32 Ex. 8 ARMEEN DM18D-HOAc/BRIJ 58 5 5 33Ex. 9 ARMEEN DM18D-HOAc/BRIJ 76 4 5 Comparative Example A 0 3Comparative Example B 1 5 Untreated Control 0 0

[0112] Tables 2 and 3 showed the overall repellency of the examples ofthe present invention were superior to those of Comparative Examples Aand B.

Examples 34-43

[0113] Details for the carpet preparation for Example 34 are as follows.DuPont 2615 nylon-6,6 BCF fiber was tufted into a level loopconstruction of 1020 g/m² (30 oz/yd²). The carpet was dyed to a beigecolor using conventional dyes and processes. The dyed carpet was treatedwith 4% SR-500 stainblocker (from E. I. du Pont de Nemours and Co. Inc.,Wilmington, Del.) by weight of carpet fiber from a bath containing 14g/L of SR-500 at pH 2.0 followed by steaming in a saturated verticalsteamer for 90 seconds, rinsing with water, and vacuum drying toapproximately 50% wet pick up. The dyed and stainblocker-treated carpetwas dried in a gas-fired oven at approximately 140° C. (280° F.). Thecarpet was cut into 28.6 cm by 26.7 cm sized samples (762 cm2) prior toprotectant application. Examples 35-43 were conducted using the aboveprocedure.

[0114] The application of the partially fluorinated urethane dispersionwas made according to the procedures of Examples 25-33. A 762 cm² carpetsample was moistened with 10 g of water using a trigger sprayer from WBBottle Supply Co., Inc., Milwaukee, Wis. The carpet sample was thensprayed using a trigger sprayer with 22 g of a mixture of 2.5 g of thepartially fluorinated urethane polymer dispersion (as shown in Tables 2and 3) and 100 g of water or approximately 25% wet pick up based on theface weight of the carpet. The surface pile of the carpet was rolledwith a small roller (7 cm wide) to mechanically spread the partiallyfluorinated urethane polymer dispersion coating across the entire carpetpile. The carpet sample was dried an oven at 65° C. for 20 minutes thenimmediately placed in a second oven at 150° C. and cured for 3 minutes.The carpet was cooled and conditioned for at least 4 hours atapproximately 22° C. and 75% relative humidity prior to any evaluations.

[0115] The calculated fluorine level was 680 micrograms of fluorine pergram of carpet fiber pile based on the 0.62% application rate of thepartially fluorinated urethane polymer dispersion onto the carpet pile,of an emulsion with a fluorine level of 11% by weight. The 0.62%application rate onto the carpet pile is the product of 25% wet pick upof the 2.5% bath of the partially fluorinated urethane polymerdispersion in water.

[0116] Aqueous dispersions of examples 10-18 were applied tostain-resistant (previously treated with 4% SR-500, available from E. I.du Pont de Nemours and Co. Inc., Wilmington, Del.) 2615 level loop dyedfirst light carpet samples by procedures described above. These sampleswere tested for their resistance to soiling using Test Method 1 versus acarpet sample treated with Comparative Example B. Example 43 representsa similar test versus Comparative Example A. The results of these testsare presented in Table 4. TABLE 4 Comparison of resistance to soilingDispersion Example Used Surfactants Delta E 34 Ex. 10 ARQUAD 2C-75/MAPEG15.7 600MS 35 Ex. 11 ARQUAD 2C-75/BRIJ 58 15.5 36 Ex. 12 ARQUAD2C-75/BRIJ 35 15.3 37 Ex. 13 ARQUAD 2HT-75/BRIJ 58 14.7 38 Ex. 14 ARMEENDM18D-HOAc/BRIJ 16.4 58 39 Ex. 15 ARQUAD 2HT-75/MERPOL SE 16.1 40 Ex. 16ARMEEN DM12D-HOAc/BRIJ 15.3 58 41 Ex. 17 ARQUAD 18-50/BRIJ 58 16.8 42Ex. 18 ETHOQUAD C/25/BRIJ 58 16.0 Comparative Example B 22.7 43 Ex. 13ARQUAD 2HT-75/BRIJ 58 16.1 Comparative Example A 16.4

[0117] The soil-resistance imparted by the compositions of the presentinvention was superior to that imparted by Comparative Examples A and B.

Examples 44-47

[0118] Aqueous dispersions of examples 10, 13, and 15 were applied tostain-resistant (previously treated with 4% SR-500) 2615 level loop dyedfirst light carpet samples by procedures described above in Examples39-48. These samples were tested for their repellency (using Test Method2) and resistance to staining (using Test Method 3) versus a carpetsample treated with Comparative Example B. Example 47 representsrepellency tests versus Comparative Example A. The results of thesetests are presented in Table 5. TABLE 5 Comparison of repellency andresistance to staining Ex. Dipersion Tip # Used Surfactants OR WR KAStain 44 Ex. 10 ARQUAD 2C-75/MAPEG 6 6 10 No 600MS 45 Ex. 13 ARQUAD2HT-75/BRIJ 58 6 6 10 No 46 Ex. 15 ARQUAD 2HT-75/MERPOL 6 6 9.5 No SEComparative Example B 5 6 8 Yes 47 Ex. 13 ARQUAD 2HT-75/BRIJ 58 6 6 NTNT Comparative Example A 3 4 NT NT

[0119] Table 5 showed that the examples of the present invention showedexcellent repellency and superior stain resistance (including no tipstaining) when compared to Comparative Example B, and superiorrepellency when compared to Comparative Example A.

Examples 48-53

[0120] Aqueous dispersions of examples 19-24 were applied tostain-resistant (previously treated with 4% SR-500, available from E. I.du Pont de Nemours and Co., Inc., Wilmington, Del.) 2615 level loop dyedfirst light carpet samples by procedures described above in Examples34-43. These samples were tested for their repellency (using Test Method2), resistance to staining (using Test Method 3), and soil-resistance(using Test Method 1) versus a carpet sample treated with ComparativeExample A. The results of these tests are presented in Table 6. TABLE 6Comparison of repellency, resistance to staining, and soil-resistanceEx. Dispersion # Used Surfactants OR WR KA Delta E 48 Ex. 19 ARQUAD2C-75/MAPEG 6 6 5 16.7 600MS 49 Ex. 20 ARQUAD 2C-75/MAPEG 6 6 6 16.4600MS 50 Ex. 21 ARQUAD 20-75/MAPEG 5 6 6 15.4 600MS 51 Ex. 22 ARQUAD2C-75/MAPEG 6 5 6 15.0 600MS 52 Ex. 23 ARQUAD 2C-75/MAPEG 6 5 5 15.1600MS 53 Ex. 24 ARQUAD 20-75/MAPEG 6 6 2 16.0 600MS Comparative ExampleA 2 4 4 17.2

[0121] Table 6 demonstrates that the examples of the present invention,over a range of cationic and non-ionic surfactant levels, had superiorrepellency, stain-resistance, and soil-resistance to those imparted byComparative Example A.

Comparative Examples H-L

[0122] Aqueous dispersions of Comparative Examples H-L were applied to1150 light blue, cut pile, stain-resistant (previously treated with 4%SR-500, available from E. I. du Pont de Nemours and Co., Inc.,Wilmington, DE) carpet samples by procedures described above in Examples25-33. These samples were tested for their repellency (using Test Method2) and resistance to staining (using Test Method 3) versus carpetsamples treated with Comparative Example A and B. The results of thesetests are presented in Table 7. TABLE 7 Comparison of repellency,resistance to staining, and soil-resistance Comp. Dispersion Tip ExampleUsed Surfactant OR WR KA Stain H Ex. C ARQUAD 18-50 1 5 6 Yes I Ex. DARQUAD 2C-75 3 6 5 Yes J Ex. E ARQUAD 2HT-75 3 6 7 Yes K Ex. F ETHOQUAD18/25 2 4 5 Yes L Ex. G ARMEEN DM18D/ 3 5 6 Yes HOAc Comparative ExampleA 0 3 9 No Comparative Example B 3 6 6 Yes

[0123] Table 7 demonstrates that the repellency and stain-resistance ofComparative Examples H-L, dispersed with only cationic surfactants, werecomparable to those of Comparative Example B containing a partiallyfluorinated urethane polymer outside of the present invention. Comparedto Comparative Example A containing an anionic surfactant, superiorrepellency was off-set by poorer stain-resistance. Thus, both thepartially fluorinated urethane polymer and the cationic/nonionicsurfactant system of the present invention are important to obtainsuprior repellency.

Example 54

[0124] A solution/mixture of 192 grams of MIBK and 208 grams ofpartially fluorinated urethane polymer described in Example 1 was meltedat about 60° C. A warm surfactant solution was prepared by mixing 8.32grams of ARQUAD 2C-75 and 2.08 grams of MAPEG 600MS with 351.52 grams ofdeionized water. This aqueous surfactant solution was combined with themolten MIBK/partially fluorinated urethane polymer mixture. Thiscomposition was then mixed in a blender and emulsified via ahomogenizer. MIBK was removed by vacuum distillation to produce a milkydispersion that was diluted to 24% solids.

Examples 55-64

[0125] The procedures described above for Example 54 was followed toproduce Examples 55-64 using different combinations of surfactants. Thesurfactants used are listed in Table 8. TABLE 8 Surfactants used in thepreparation of Examples 55-64. Cationic Amount Non-ionic Amount Ex. #Surfactant (g) Surfactant (g) 55 ARQUAD 2HT-75 8.32 MERPOL SE 2.19 56ARQUAD 2HT-75 8.32 BRIJ 58 2.08 57 ARQUAD 2C-75 13.87 MAPEG 4.16 58ARQUAD 2C-75 13.87 MAPEG 1.04 59 ARQUAD 2C-75 5.55 MAPEG 4.16 60 ARQUAD2C-75 5.55 MAPEG 1.04 61 ARQUAD 2HT-75 13.87 BRIJ 58 4.16 62 ARQUAD2HT-75 13.87 BRIJ 58 1.04 63 ARQUAD 2HT-75 5.55 BRIJ 58 4.16 64 ARQUAD2HT-75 5.55 BRIJ 58 1.04

Examples 65-67

[0126] Aqueous dispersions of examples 54-56 were applied tostain-resistant (previously treated with 4% SR-500, available from E. I.du Pont de Nemours and Co., Inc., Wilmington, Del.) 2615 level loop dyedfirst light carpet samples by procedures described above in Examples34-43. These samples were tested for their resistance to staining (usingTest Method 3) versus a carpet sample treated with Comparative ExampleB. The results of these tests are presented in Table 9. TABLE 9Comparison of resistance to staining Dispersion Example Used SurfactantsKA 65 Ex. 54 ARQUAD 2C-75/MAPEG 600MS 66 Ex. 55 ARQUAD 2HT-75/MERPOL SE8 67 Ex. 56 ARQUAD 2HT-75/BRIJ 58 8 Comparative Example B 7

[0127] Table 9 demonstrates that the compositions of the presentinvention showed superior stain resistance when compared to ComparativeExample B.

Examples 68-72

[0128] Aqueous dispersions of examples 54 and 57-60 were applied tostain-resistant (previously treated with 4% SR-500, available from E. I.du Pont de Nemours and Co., Inc., Wilmington, Del.) 2615 level loop dyedfirst light carpet samples by procedures described above in Examples34-43. These samples were tested for resistance to soiling (using TestMethod 1) versus a carpet sample treated with Comparative Examples A.The results of these tests are presented in Table 10. TABLE 10Comparison of repellency Dispersion Example used Surfactants Delta E 68Ex. 54 ARQUAD 2HT-75/BRIJ 58 16.75 69 Ex. 57 ARQUAD 2HT-75/BRIJ 58 16.9570 Ex. 58 ARQUAD 2HT-75/BRIJ 58 16.90 71 Ex. 59 ARQUAD 2HT-75/BRIJ 5816.01 72 Ex. 60 ARQUAD 2HT-75/BRIJ 58 15.87 Comparative Example A 18.77

[0129] Table 10 demonstrates that the compositions of the presentinvention showed superior soil resistance when compared to ComparativeExample A.

Examples 73-77

[0130] Aqueous dispersions of examples 56 and 61-64 were applied tostain-resistant (previously treated with 4% SR-500, available from E. I.du Pont de Nemours and Co., Inc., Wilmington, Del.) 2615 level loop dyedfirst light carpet samples by procedures described above in Examples34-43. These samples were tested for repellency (using Test Method 2)versus a carpet sample treated with Comparative Examples A. The resultsof these tests are presented in Table 11. TABLE 11 Comparison ofRepellency Dispersion Example used Surfactants OR WR 73 Ex. 56 ARQUAD2HT-75/BRIJ 58 6 6 74 Ex. 61 ARQUAD 2HT-75/BRIJ 58 6 5 75 Ex. 62 ARQUAD2HT-75/BRIJ 58 6 5 76 Ex. 63 ARQUAD 2HT-75/BRIJ 58 6 5 77 Ex. 64 ARQUAD2HT-75/BRIJ 58 5 4 Comparative Example A 0 3

[0131] Table 11 demonstrates that the compositions of the presentinvention showed significantly superior repellency when compared toComparative Example A.

Example 78

[0132] The compatibility of the partially fluorinated urethane polymerdispersions of the present invention was tested as described in TestMethod 4, above. The results are shown in Table 12. TABLE 12Compatibility Testing Commercial Anionic Protectants DuPont DuPontDuPont Example # N-119 N140 SR-500 DISPERSION OF THE PRIOR ARTComparative Example B Separated Gelled Separated DISPERSIONS OF THEPRESENT INVENTION Example 21 OK OK OK Example 22 OK OK OK

[0133] Table 12 shows the incompatibility of commercial anionicprotectants and Comparative Example B (a cationic dispersion of theprior art). The same commercial anionic protectants were compatibleExamples 21 and 22 of the present invention.

Example 79-80

[0134] A dyed light tan 30 oz./yd² (1 kg/m²) tufted, level loop pilecarpet (made from twisted, SUPERBA heatset, 2615 DuPont fiber, from E.I. du Pont de Nemours and Company, Wilmington, Del.) was passed througha flex-nip application of 250% by weight of a bath containing 16 g/L ofSR-500 Stain Resist (available from E. I. du Pont de Nemours and Co.Inc., Wilmington, Del.). The carpet was steamed at 210-212° F. (99-100°C.) for 2.5 min. and washed with water. It was then vacuum extracted to50% wet pickup, and dried to a carpet face temperature of 300° F. (149°C.).

[0135] The carpet sample was then sprayed using a trigger sprayer with22 g of a mixture of 0.45 g of the partially fluorinated urethanepolymer dispersion prepared according to the procedure of Example 56 and100 g of water or approximately 22% wet pick up based on the face weightof the carpet. The surface pile of the carpet was rolled with a smallroller (7 cm wide) to mechanically spread the partially fluorinatedurethane polymer dispersion coating across the entire carpet pile. Thecarpet sample was dried an oven at 65° C. for 20 minutes thenimmediately placed in a second oven at 150° C. and cured for 3 minutes.The carpet was cooled and conditioned for at least 4 hours atapproximately 22° C. and 75% relative humidity prior to any evaluations.

[0136] The goal fluorine level was 105 micrograms/gram based on the 0.1%application rate of the partially fluorinated urethane polymerdispersion onto the carpet pile, an emulsion with a fluorine level of10.5% by weight. The 0.1% application rate of partially fluorinatedurethane polymer dispersion onto the carpet pile was calculated as theproduct of 22% wet pick up of the 0.45% application bath of thedispersion in water. The carpet fiber from this treated sample wasanalyzed according to AATCC test method 189 and showed 130micrograms/gram fluorine on the carpet fiber with an accuracy of +/−80micrograms/gram fluorine. These samples were tested for oil and waterrepellency and soil resistance using Test Methods 1 and 2. The resultsare shown in Table 13. TABLE 13 Performance Versus Prior Art at LowerTreatment Levels Ex. Dispersion Delta Goal F # used Surfactants OR WR EF* found* 79 Ex. 56 ARQUAD 2HT- 4 4 16.8 100 132 75/BRIJ 58 80 Ex. 13ARQUAD 2HT- 4 4 16.4 100 152 75/BRIJ 58 Comparative Example A 3 4 16.4600 654 Untreated Control 0 0 20.7 0 29

[0137] Table 13 shows that carpet samples treated with significantlylower quantities of the dispersions of the present invention displayedrepellency and soil-resistance equivalent to, if not better than, thatprovided by a much greater quantity of the prior art (ComparativeExample A). Even at these reduced levels of application, dramaticimprovements in performance over the untreated control was imparted.

What is claimed is:
 1. An aqueous dispersion comprising A. a partiallyfluorinated urethane polymer having at least one urea linkage, whichcompound is the product of the reaction of: (1) at least one organicpolyisocyanate containing at least three isocyanate groups; (2) at leastone fluorochemical compound which contains per molecule (a) a singlefunctional group having one or more Zerewitinoff hydrogen atoms and (b)at least two carbon atoms, each of which is attached to at least twofluorine atoms; and (3) water in an amount sufficient to react with fromabout 5% to about 60% of the isocyanate groups in said polyisocyanate;B. a non-fluorinated cationic surfactant; and C. a non-fluorinatednonionic surfactant.
 2. The dispersion of claim 1 wherein the cationicsurfactant is selected from the group consisting of salts of protonatedamines, quaternary ammonium salts, and amine oxides.
 3. The dispersionof claim 2 wherein the cationic surfactant is selected from the groupconsisting of at least o ne of a protonated alkyl dimethyl amine salt,protonated dialkyl methyl amine salt, protonated alkyl ethoxylated aminesalt, protonated alkyl diamine salt, protonated alkyl ethoxylateddiamine salt, alkyl trimethyl ammonium salt, dialkyl dimethyl ammoniumsalt, alkyl methyl ethoxylated ammonium salt, alkyl dimethyl benzylammonium salt, dialkyl methyl benzyl ammonium salt, alkyl pyridiniumsalt, alkylamidomethylpyridinium salt, carboalkoxy pyridinium salt,alkyl quinolinium salt, alkyl isoquinolinium salt, N,N-alkylmethylpyrollidinium salt, amidoimidazolium salt, amido ammonium salt,quaternary ammonium salt of alkyl diamine, ethoxylate of a quaternaryammonium salt of alkyl diamine, alkyl dimethyl amine oxide, dialkylmethyl amine oxide, and alkyl diamine oxide.
 4. The dispersion of claim3 wherein the cationic surfactant is dialkyl dimethyl ammonium chloride.5. The dispersion of claim 1 wherein the nonionic surfactant is acondensate with ethylene oxide of at least one of a fatty acid alkanolamide, an alkyl phenol, a fatty acid, a fatty alcohol, an ester of afatty acid and polyhydric alcohol, and a polyoxypropylene blockcopolymer.
 6. The dispersion of claim 5 wherein the nonionic surfactantis of the formula A C_(x)H_((2x+1))O—(CH₂CH₂O)_(n)—H  A wherein x is 12to 18 and n is 5 to
 100. 7. The dispersion of claim 6 wherein thenonionic surfactant is a polyethoxylated linear alcohol.
 8. Thedispersion of claim 1 wherein the cationic surfactant is selected fromthe group consisting of salts of protonated amines, quaternary ammoniumsalts, and amine oxides, and the nonionic surfactant is a condensatewith ethylene oxide of at least one of a fatty acid alkanol amide, analkyl phenol, a fatty acid, a fatty alcohol, an ester of a fatty acidand polyhydric alcohol, and a polyoxypropylene block copolymer.
 9. Thedispersion of claim 8 wherein the cationic surfactant is dialkyldimethyl ammonium chloride and the non-ionic surfactant is apolyethoxylated linear alcohol.
 10. The dispersion of claim 1 whereinthe amount of surfactant is from about 1.5% to about 8% by weight basedon the amount of the partially fluorinated urethane polymer.
 11. Thedispersion of claim 1 wherein the amount of water is sufficient to reactwith about 15% to about 30% of said isocyanate groups.
 12. Thedispersion of claim 1 wherein the polyisocyanate is selected from thegroup consisting of hexamethylene diisocyanate homopolymer, hydrocarbondiisocyanate-derived trimer, isocyanate trimer of toluene diisocyanate,and isocyanate trimer of 3-isocyanato-methyl-3,4,4-trimethylcyclohexylisocyanate.
 13. The dispersion of claim 1 wherein said fluorochemicalcompound which contains a single functional group is represented by theformula: R^(f)—R_(k)—X—H in which R^(f) is a monovalent aliphatic groupcontaining at least two carbon atoms each of which is attached to atleast two fluorine atoms; R is a divalent organic radical; k is 0 or 1;and X is —O—, —S—, or —N(R³)— in which R³ is H, alkyl containing 1 to 6carbon atoms or a R^(f)—R_(k)— group.
 14. The dispersion of claim 1wherein said fluorochemical compound which contains a single functionalgroup is represented by the formula: R^(f)—(CH₂)_(q)—X—H in which R^(f)is a mixture of perfluoroalkyl groups, CF₃CF₂(CF₂)_(r) in which r is 2to 18; and q is 1, 2 or
 3. 15. The dispersion of claim 14 wherein R^(f)is a mixture of said perfluoroalkyl groups, CF₃CF₂(CF₂)_(r); and r is 2,4, 6, 8, 10, 12, 14, 16, and
 18. 16. The dispersion of claim 14 whereinX is oxygen and q is
 2. 17. The dispersion of claim 1 wherein saidfluorochemical compound which contains a single functional group isrepresented by the formula: R^(f)—R_(k)—R²—X′—H wherein R^(f) is amonovalent aliphatic group containing at least two carbon atoms each ofwhich is attached to at least two fluorine atoms; R is the divalentradical: —C_(m)H_(2m)SO—, —C_(m)H_(2m)SO₂—, —SO₂N(R³)—, or —CON(R³)— inwhich m is 1 to 22 and R³ is H or alkyl of 1 to 6 carbon atoms; k is 0or 1; R² is the divalent linear hydrocarbon radical: —C_(n)H_(2n)— whichcan be optionally end-capped by

n is 0 to 12, p is 1 to 50, and R⁴, R⁵ and R⁶ are the same or differentH or alkyl containing 1 to 6 carbon atoms; and X′ is —O—, —S—, or—N(R⁷)— in which R⁷ is H, alkyl containing 1 to 6 carbon atoms or aR^(f)—R_(k)—R²— group.
 18. The dispersion of claim 1 additionallycomprising a non-fluorinated organic compound represented by theformula: R¹⁰—(R¹¹)_(k)—YH wherein R¹⁰ is a C₁-C₁₈ alkyl, a C₁-C₁somega-alkenyl radical or a C₁-C₁₈ omega-alkenoyl; R¹¹ is

R⁴, R⁵ and R⁶ are the same or different H or alkyl radical containing 1to 6 carbon atoms and p is 1 to 50; k is 0 or 1; and Y is —O—, —S—, or—N(R³)— in which R³ is H or alkyl containing 1 to 6 carbon atoms.
 19. Amethod for providing water and oil repellency to a substrate comprisingapplication to the substrate of an aqueous dispersion comprising A. apartially fluorinated urethane polymer having at least one urea linkage,which compound is the product of the reaction of: (1) at least oneorganic polyisocyanate containing at least three isocyanate groups; (2)at least one fluorochemical compound which contains per molecule (a) asingle functional group having one or more Zerewitinoff hydrogen atomsand (b) at least two carbon atoms, each of which is attached to at leasttwo fluorine atoms; and (3) water in an amount sufficient to react withfrom about 5% to about 60% of the isocyanate groups in saidpolyisocyanate; B. a non-fluorinated cationic surfactant; and C. anon-fluorinated nonionic surfactant.
 20. The method of claim 19 whereinthe dispersion contains a cationic surfactant selected from the groupconsisting of salts of protonated amines, quaternary ammonium salts, andamine oxides, and the nonionic surfactant is a condensate withpolyethylene oxide of at least one of a fatty acid alkanol amide, analkyl phenol, a fatty acid, a fatty alcohol, an ester of a fatty acidand polyhydric alcohol, and a polyoxypropylene block copolymer.
 21. Themethod of claim 20 wherein the dispersion contains a cationic surfactantwhich is dialkyl dimethyl ammonium chloride and the non-ionic surfactantis a polyethoxylated linear alcohol.
 22. The method of claim 19 whereinthe dispersion is applied at a rate sufficient to provide from about 100micrograms to about 2000 micrograms fluorine per gram of dry substratefiber.
 23. The method of claim 19 wherein the dispersion is applied byspraying or foaming.
 24. The method of claim 19 wherein the dispersionis co-applied with a composition which provides stain resistance.
 25. Asubstrate treated with an aqueous dispersion comprising A. a partiallyfluorinated urethane polymer having at least one urea linkage, whichcompound is the product of the reaction of: (1) at least one organicpolyisocyanate containing at least three isocyanate groups; (2) at leastone fluorochemical compound which contains per molecule (a) a singlefunctional group having one or more Zerewitinoff hydrogen atoms and (b)at least two carbon atoms, each of which is attached to at least twofluorine atoms; and (3) water in an amount sufficient to react with fromabout 5% to about 60% of the isocyanate groups in said polyisocyanate;B. a non-fluorinated cationic surfactant; and C. a non-fluorinatednonionic surfactant.
 26. The substrate of claim 25 which is a carpet.27. The substrate of claim 25 having a coating on the surface thereofcomprising a dispersion of claim 1 and at least one stainblocker. 28.The substrate of claim 25 having a coating on the surface thereofcontaining from about 100 micrograms to about 2000 micrograms fluorineper gram of dry substrate fiber.
 29. The substrate of claim 26 which isnylon, polyester, polyolefin, wool, polytrimethylene terephthalate,cotton, jute or sisal.